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WO2006018866A1 - Inhibiteur de croissance de bactérie oxydant le soufre et méthode de prévention de la corrosion du béton - Google Patents

Inhibiteur de croissance de bactérie oxydant le soufre et méthode de prévention de la corrosion du béton Download PDF

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Publication number
WO2006018866A1
WO2006018866A1 PCT/JP2004/011814 JP2004011814W WO2006018866A1 WO 2006018866 A1 WO2006018866 A1 WO 2006018866A1 JP 2004011814 W JP2004011814 W JP 2004011814W WO 2006018866 A1 WO2006018866 A1 WO 2006018866A1
Authority
WO
WIPO (PCT)
Prior art keywords
concrete
growth inhibitor
sulfur
powder
corrosion
Prior art date
Application number
PCT/JP2004/011814
Other languages
English (en)
Japanese (ja)
Inventor
Terunobu Maeda
Original Assignee
Civil Chemical Engineering Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Civil Chemical Engineering Co., Ltd. filed Critical Civil Chemical Engineering Co., Ltd.
Priority to PCT/JP2004/011814 priority Critical patent/WO2006018866A1/fr
Publication of WO2006018866A1 publication Critical patent/WO2006018866A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/06—Aluminium; Calcium; Magnesium; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/60—Agents for protection against chemical, physical or biological attack
    • C04B2103/61—Corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/60—Agents for protection against chemical, physical or biological attack
    • C04B2103/67—Biocides

Definitions

  • the present invention relates to a growth inhibitor of sulfur-oxidizing bacteria such as the genus Thiobacillus causing corrosion of concrete in a sewage treatment facility or a sewage pipe, and a method for preventing corrosion of concrete using the inhibitor. About.
  • Conventional methods for preventing corrosion of concrete structures include, for example, a method in which a metal or metal oxide that is insoluble in water such as nickel and soluble in sulfuric acid is used as an active ingredient and is directly mixed with concrete (Patent Document 1), Or insoluble in sulfuric acid such as W, Mo, Na WO, Na MoO
  • Patent Document 2 There has been proposed a method (Patent Document 2) in which a metal and a metal compound are used as active ingredients and added during the production of a concrete structure.
  • Patent Document 3 discloses a formic acid compound such as formic acid, sodium formate or calcium formate as an active ingredient that suppresses the growth of sulfur-oxidizing bacteria and exhibits a corrosion-inhibiting action on concrete. Has been proposed.
  • the formic acid or the formic acid compound described in this document is readily water-soluble or liquid, and even in the examples, calcium formate is dissolved in water and the effect of inhibiting the growth of sulfur-oxidizing bacteria is shown. Absent. Therefore, when such a readily water-soluble or liquid compound is used as an effective component, it is not possible to expect a long-term concrete corrosion prevention effect, and it is also necessary to increase the amount of use.
  • formic acid or a salt thereof can be used as a cement admixture used for rapid-hardening cement and the like because it exhibits a pseudo-coagulation action in a cement composition as shown in Patent Documents 4-16. ing. Furthermore, pasture preservatives that utilize the growth inhibition effect of microorganisms by formic acid or ammonium formate are also commercially available.
  • Patent Document 1 Japanese Patent Laid-Open No. 4-149053
  • Patent Document 3 Japanese Patent Laid-Open No. 10-324549
  • Patent Document 4 JP-A-8-310845
  • Patent Document 5 Japanese Patent Laid-Open No. 2001-48617
  • Patent Document 6 Special Table 2001-509124
  • An object of the present invention is to provide a sulfur-oxidizing bacterium growth inhibitor capable of sufficiently inhibiting the growth of sulfur-oxidizing bacteria for a long period of time, wherein the active ingredient is a poorly water-soluble powder.
  • Another object of the present invention is to provide a method for preventing corrosion of concrete, which can sufficiently prevent corrosion of concrete in a sewage treatment facility by sulfur-oxidizing bacteria over a long period of time and has almost no risk of reducing the strength of the concrete. There is.
  • the magnesium oxide having a solubility power in water of 25 ° C of S3.0g / I00ml or less.
  • a sulfur-oxidizing bacterial growth inhibitor containing, as an active ingredient, a magnesium formate-containing powder obtained by reacting shim and formic acid.
  • a method for preventing corrosion of a concrete comprising a step of mixing the sulfur-oxidizing bacteria growth inhibitor in producing a concrete by curing a cement composition containing cement and aggregate.
  • the growth inhibitor of the present invention comprises a magnesium formate-containing powder having low water solubility and poorly water solubility as an active ingredient, and therefore can sufficiently inhibit the growth of sulfur-oxidizing bacteria over a long period of time.
  • the method for preventing corrosion of concrete according to the present invention uses the growth inhibitor of the present invention, the corrosion of concrete by sulfur-oxidizing bacteria and the like is sufficiently inhibited over a long period of time by adding a small amount to the concrete in a sewage treatment facility or the like.
  • the effect can be obtained with a small amount of blending, the corrosion prevention effect can be obtained without substantially reducing the strength of the concrete itself.
  • FIG. 1 is a graph showing the results of measuring the effect of active ingredients in the growth inhibitor of the present invention on the growth of the NB1-3 strain carried out in Examples 1 and 2 and Comparative Example 1.
  • FIG. 2 is a graph showing the results of measuring the effect of the active ingredient in the growth inhibitor of the present invention on the elemental sulfur oxidation activity of A. ferrooxidans ATCC2370 strain carried out in Examples 3-5 and Comparative Example 2.
  • FIG. 3 is a graph showing the results of measuring the effect of active ingredients in the growth inhibitor of the present invention on the elemental sulfur oxidation activity of NB1-3 strain washed cells performed in Examples 6 and 7 and Comparative Example 3.
  • the growth inhibitor of the present invention is, for example, an inhibitor that inhibits the growth of sulfur-oxidizing bacteria such as Cibacillus, which cause corrosion of concrete in sewage treatment facilities, and is not limited to concrete in contact with sewage. Effectively inhibit the growth of sulfur-oxidizing bacteria even in concrete that is close to sewage treatment facilities and is affected by atmospheric hydrogen sulfide. Can do.
  • sulfur-oxidizing bacteria such as Cibacillus
  • the active ingredient used in the growth inhibitor of the present invention is a poorly water-soluble magnesium formate-containing powder obtained by reacting magnesium oxide and formic acid.
  • the solubility of the powder in water at 25 ° C. is usually 3.0 gZl00 ml or less, preferably 2.0 g / l00 ml or less, particularly preferably 1.7 g / 100 ml or less, and its lower limit is usually 0.2 gZl00 ml or more. When the solubility exceeds 3.0 g / 100 ml, there is a possibility that the growth inhibitory effect over a long period cannot be expected.
  • the particle size of the magnesium formate-containing powder is not particularly limited.
  • the growth inhibiting action can be effectively exhibited, and the particle size blended at a desired position in the concrete is preferable. .
  • 0.1 100 II m is desirable.
  • magnesium oxide and formic acid are reacted. Since this reaction is an exothermic reaction, it is usually preferable to carry out the reaction while cooling to about 0-5 ° C.
  • the reaction product can be obtained by pulverizing the reaction product by operations such as grinding, etc., and further drying and the like when the exotherm has subsided.
  • the powdering operation usually re-heats due to powdering, so it is preferable to continue the operation until there is no heat generation.
  • hydration can be carried out by adding water before pulverization.
  • the amount charged in the reaction of magnesium oxide and formic acid is usually such that the ratio of magnesium oxide: formic acid is about 1: 2-4.
  • the product obtained by the reaction is a mixture of magnesium formate and magnesium hydroxide.
  • the anhydrous salt of magnesium formate is usually dissolved in about 14.0 g in 100 ml of water at 0 ° C.
  • the solubility of the magnesium formate-containing powder is considerably low as described above. This is presumed that the reaction product magnesium formate was contaminated with magnesium hydroxide and stabilized.
  • the sulfur-oxidizing bacterium that inhibits growth by the growth inhibitor of the present invention includes a sulfur-oxidizing bacterium of the genus Cibacillus, such as Thiobacillus thioparus, T. neapolitanus, Cibacillus T. capsulatus, T. tepidarius, T. denitrificans, T. ferrooxidans, T. ferrooxidans, T. ferrooxidans, T. ferrooxidans, T. ferrooxidans ⁇ bachinoles 'thiooxidans ( ⁇ ⁇ thiooxidans), ⁇ bachinoles' Snovelas (T. novellus)
  • Cibacillus such as Thiobacillus thioparus, T. neapolitanus, Cibacillus T. capsulatus, T. tepidarius, T. denitrificans, T. ferrooxidans, T. ferrooxidans, T. ferrooxidans, T. ferrooxidans, T. ferr
  • Cibacillus 'Berstus ( ⁇ versutus), Cibacillus' Intermediaus (ius ⁇ intermedius), Cibacillus. T. americanus, Cibacillus.
  • the effective concentration of the growth inhibitor of the present invention is not particularly limited, and can be appropriately selected depending on the kind of sulfur-oxidizing bacteria. However, it is usually preferably O.OlgZkg or more, particularly preferably 0.150 g / kg.
  • the method for preventing corrosion of concrete according to the present invention includes a step of mixing the sulfur-oxidizing bacterial growth inhibitor of the present invention when a concrete is produced by curing a cement composition containing cement and aggregate.
  • the cement composition is not particularly limited as long as it is a cement composition used when producing concrete, and can be appropriately selected according to a known composition and according to a desired structure. At this time, various additives may be included in order to obtain a desired concrete structure.
  • the mixing ratio of the growth inhibitor of the present invention is sufficient to prevent corrosion even when the amount is usually 0.0001-0.1 part by weight, particularly 0.0001-0.01 part by weight, per 100 parts by weight of cement in the cement composition. As well as being obtained, the effect can be sustained significantly.
  • the growth inhibitor of the present invention After the growth inhibitor of the present invention has been mixed into the cement composition, concrete having an excellent anticorrosion action can be obtained by molding and curing, for example, by a known method. In particular, it is possible to easily and evenly mix the growth inhibitor of the present invention into concrete even by centrifugal molding.
  • This centrifugal molding method can be performed in the same manner as a method for producing a known fume tube or the like, and concrete having a desired growth inhibitor can be obtained by appropriately selecting the centrifugal molding conditions.
  • the particle size of the growth inhibitor is important. If the particle size is too small, it may move together with the breathing water used during centrifugal molding and may be drained in some cases. If the particle size is too large, it may move to the outer surface during centrifugal molding. Therefore, the particle size of the magnesium formate-containing powder as the active ingredient is preferably selected from the above-mentioned preferred range.
  • Corrosive concrete l.Og was inoculated into 20 ml of machine salt medium (pH 7.0) and stored under aerobic conditions at 30 ° C. When the pH of the medium dropped to 2.0, the medium was changed and this culturing operation was performed 5 times. A yellow colony of Cibacillus thixoxidans obtained by roasting was isolated, and this isolate was designated as NB 1-3.
  • Example 1 The powder (A) 5 mg (Example 1), the power to add lOOmg (Example 2), or the control powder was not added (Comparative Example DNB1-3 strain was cultured. The amount of growth of NB1-3 strain was measured by absorbance at 660. The results are shown in FIG.
  • Fig. 1 shows that powder (A) exhibits excellent sulfur-oxidizing bacteria growth inhibitory activity.
  • reaction vessel of a Workbruda pressure gauge equipped with a manometer, reaction vessel and shaking device 5 mg of A.ferrooxidans ATCC 2370 strain, a commercially available sulfur-oxidizing bacterium, ⁇ -alanine-SO 2 _ loose
  • Impregnation solution 200 ⁇ 1 ( ⁇ 3.0) and sodium sulfite 200 ⁇ mol were added in a total volume of 3 ml, and the powder prepared in Example 1 (A) 0.5 mg (Example 3), 5.3 mg Example 4), 30 mg (Example 5) was added or was not added as a control (Comparative Example 2), and the amount of oxygen absorbed over time was measured. Place 0.2 ml of sodium hydroxide in the centerwell and adjust the pH in the reaction tank to 3.0. The measurement was performed while adjusting to. The gas phase of the Workbruda pressure gauge was kept at 30 ° C with air. The result is shown in figure 2.
  • powder (A) exhibits excellent sulfur-oxidizing bacterial growth inhibitory activity under acidic pH 3.0.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Zoology (AREA)
  • Ceramic Engineering (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L’invention concerne un inhibiteur de croissance de bactérie oxydant le soufre comprenant une poudre difficilement soluble dans l’eau comme ingrédient actif et capable d’inhiber de manière satisfaisante la croissance de bactéries oxydant le soufre pendant une période prolongée ainsi qu’une méthode de prévention de la corrosion de béton selon laquelle la corrosion du béton par des bactéries oxydant le soufre peut être empêchée de manière satisfaisante sur une période prolongée et ne comportant pratiquement pas de danger de détérioration de la force du béton. Cet inhibiteur présente une solubilité dans l’eau de 3 g/100 ml ou moins à 25°C et comprend une poudre comportant du formiate de magnésium obtenue en faisant réagir de l’oxyde de magnésium avec de l’acide formique comme ingrédient actif. La méthode de prévention de la corrosion de béton utilise cet inhibiteur.
PCT/JP2004/011814 2004-08-18 2004-08-18 Inhibiteur de croissance de bactérie oxydant le soufre et méthode de prévention de la corrosion du béton WO2006018866A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2004/011814 WO2006018866A1 (fr) 2004-08-18 2004-08-18 Inhibiteur de croissance de bactérie oxydant le soufre et méthode de prévention de la corrosion du béton

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2004/011814 WO2006018866A1 (fr) 2004-08-18 2004-08-18 Inhibiteur de croissance de bactérie oxydant le soufre et méthode de prévention de la corrosion du béton

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WO2006018866A1 true WO2006018866A1 (fr) 2006-02-23

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010106121A1 (fr) * 2009-03-20 2010-09-23 Basf Se Élaboration sans solvant de matériau squelette organométallique poreux à base de formiate de magnésium

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000159554A (ja) * 1998-11-24 2000-06-13 Fujita Corp コンクリート腐食防止剤およびコンクリート腐食防止用コーティング材

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000159554A (ja) * 1998-11-24 2000-06-13 Fujita Corp コンクリート腐食防止剤およびコンクリート腐食防止用コーティング材

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010106121A1 (fr) * 2009-03-20 2010-09-23 Basf Se Élaboration sans solvant de matériau squelette organométallique poreux à base de formiate de magnésium
US8431744B2 (en) 2009-03-20 2013-04-30 Basf Se Solvent-free preparation of magnesium formate-based porous metal-organic framework

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